Assignment: Physical Chemistry

ASSIGNMENT
PHYSICAL CHEMISTRY
DYNAMIC CHAIN REACTION
DYNAMIC CHAIN REACTIONS

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Chain reactions usually consist of many repeating elementary steps,
each of which has a chain carrier. Once started, chain reactions
continue until the reactants are exhausted. Fire and explosions are
some of the phenomena associated with chain reactions. The chain
carriers are some intermediates that appear in the repeating
elementary steps. These are usually free radicals.
Once initiated, repeating elementary steps continue until the reactants
are exhausted. When repeating steps generate more chain carriers,
they are called chain branching reactions, which leads to explosions.
If the repeating elementary steps do not lead to the formation of new
product, they are called chain inhibition reactions. Addition of other
materials in the reaction mixture can lead to the inhibition reaction to
prevent the chain propagation reaction. When chain carriers react with
one another forming stable product, the elementary steps are called
chain termination reactions.
Explosions, polymerizations, and food spoilage often involve chain
reactions. The chain reaction mechanism is involved in nuclear
reactors; in this case the chain carriers are neutrons. The mechanisms
describing chain reactions are useful models for describing chemical
reactions. Most chemical chain reactions have very reactive
intermediates called free radicals. The intermediate that maintains
the chain reaction is called a chain carrier. These atoms or fragments
are usually derived from stable molecules due to photo- or heat-
dissociation.
Usually, a free radical is marked by a dot beside the symbol ( ), which
represents an odd electron exists on the species. This odd electron
makes the intermediate very reactive. For example, the oxygen,
chlorine and ethyl radicals are represented by O .,Cl., and C2H5.,
respectively. The Cl. radicals can be formed by the homolytic
photodissociation reaction:
Cl2 +hv→Cl.+.Cl
Mechanism of Chain Reactions

The elementary steps used for mechanisms of chain reactions can be
grouped into the following categories:
 initiation step
 chain propagation steps
 chain branching steps
 chain inhibition steps
 chain termination steps
For example, the chlorination of ethane is a chain reaction, and its
mechanism is explained in the following way.
If we mix chlorine, Cl2, and ethane,CH3CH3 , together at room
temperature, there is no detectable reaction. However, when the
mixture is exposed to light, the reaction suddenly initiates, and
explodes. To explain this, the following mechanism is proposed.
Initiation Step
Light (hv ) can often be used to initiate chain reactions since they can
generate free radical intermediates via a photodissociation reaction.
The initiation step can be written as:
Cl2 +hv→Cl.+.Cl
Chain Propagation Step

Elementary steps in which the number of free radicals consumed is
equal to the number of free radicals generated are called chain
propagation steps. Once initiated, the following chain propagation
steps repeat indefinitely or until the reactants are exhausted:
Cl.+ H3CCH3 → ClH2CCH3+H.
Cl.+ H3CCH3 → H3CCH2.+HCl
H.+ Cl2 → HCl+Cl.
and many other possibilities.
In each of these steps, a radical is consumed, and another radical is

generated. Thus, the chain reactions continue, releasing heat and
light. The heat and light cause more radicals to form. Thus, the chain
propagation steps cause chain branching reactions.
Chain Branching Steps

Branching reactions are elementary steps that generate more free
radicals than they consume. Branching reactions result in an
explosion. For example, in the reaction between hydrogen and oxygen,
the following reaction may take place:
H.+ O2 →HO.+.O.
where .O. is a di-radical, because the atom has an electronic
configuration 2s2 2px2 2py1 2pz1 . In this elementary step, three radicals
are generated, whereas only one is consumed.
The di-radical may react with a H2 molecule to form two radicals.
. .
O +H2→HO. + H.
Thus, together chain branching reactions increase the number of

chain carriers. Branching reactions contribute to the rapid explosion
of hydrogen-oxygen mixtures, especially if the mixtures have proper
proportions.
Chain Inhibition Steps

The steps not leading to the formation of products are called
inhibition reactions or steps. For example, the following steps are
inhibition reactions.
Cl. + ClH2CCH3 → H3CCH2+Cl2
Cl. + HCl→H. + Cl2
H. + ClH2CCH3 → H3CCH3+Cl.
Furthermore, sometimes another reactive substance .A may be added

to the system to reduce the chain carriers to inhibit the chain
reactions.
Cl + .A→ClA (not reactive)
The species .A is often called a radical scavenger. In food industry,

radical scavengers are added to prevent spoilage due to oxidation;
these are called biologicaloxidants.
The mechanisms in chain reactions are often quite complicated. When

intermediates are detected, a reasonable mechanism can be proposed.
Adding radical scavenger to prevent food spoilage is an important
application in food chemistry. This application came from the
application of the chain reaction model to natural phenomena.
Chain Termination Steps

Chain termination steps are elementary steps that consume radicals.
When reactants are exhausted, free radicals combine with one another
to give stable molecules(since unpaired electrons become paired).
These elementary steps are responsible for the chain reactions'
termination:
Cl .+.Cl→Cl−Cl
H .+.H→H−H
H .+.Cl→H−Cl
H3CCH2. + .H2CCH3 →CH3CH2−CH2CH3 (forming a dimer)
and other possibilities
In chain reactions, many products are produced.
Pyrolysis of Acetaldehyde
In order for the overall kinetics to be of the three halves order,for a
first initiation reaction, the chain terminating step must be a second
order reaction between two radicals that undergo second order
propagation reactions.Example as given below:
The pyrolysis (i.e. thermal decomposition) of ethanal (acetaldehyde,

CH3CHO) is found to exhibit a simple rate law where:
Some ethane is also detected.
This reaction proceeds according the Rice-Herzfeld mechanism where:
According to steady state approximation, the net rate change of the

intermediates may be set to zero, i.e.:
i.e. (i)+(ii) =>
and hence the steady-state concentration of the methyl radical is:
i.e. from equation (b), the rate of formation of methane (i.e. the rate of
the overall reaction) is given by:
in accordance with three 3/2 order observed experimentally and
depends on the concerntration of reactant.

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ASSIGNMENT

DYNAMIC CHAIN REACTIONS

Mechanism of Chain Reactions

Chain Propagation Step

In each of these steps, a radical is consumed, and another radical is

Chain Branching Steps

Thus, together chain branching reactions increase the number of

Chain Inhibition Steps

Furthermore, sometimes another reactive substance .A may be added

The species .A is often called a radical scavenger. In food industry,

The mechanisms in chain reactions are often quite complicated. When

Chain Termination Steps

The pyrolysis (i.e. thermal decomposition) of ethanal (acetaldehyde,

Some ethane is also detected.

This reaction proceeds according the Rice-Herzfeld mechanism where:

According to steady state approximation, the net rate change of the

i.e. (i)+(ii) =>

and hence the steady-state concentration of the methyl radical is:

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